Direct intercalation of bis-2,2',2″,6-terpyridylcobalt(III) into zirconium phosphate layers for biosensing applications.

The direct intercalation reaction of [Co(tpy)(2)](2+) with the highly hydrated θ phase of layered zirconium phosphate (θ-ZrP) resulted in the formation of the oxidized [Co(tpy)(2)](3+) ion within the ZrP material. The X-ray powder diffraction patterns showed that the interlayer distance increases from 10.3 Å in θ-ZrP to 14.9 Å in the dry [Co(tpy)(2)](3+)-intercalated ZrP {[Co(tpy)(2)](3+):ZrP} phase. The complex remains electroactive within the layers of ZrP. The formal potential of a carbon paste electrode (CPE) modified with [Co(tpy)(2)](3+):ZrP (E°' = 40.8 mV versus Ag/AgCl, 3.5 M NaCl) is non-pH-dependent. However, the sensitivity of the [Co(tpy)(2)](3+):ZrP-modified CPE for the detection of reduced nicotinamide adenine dinucleotide (NADH) electrooxidation was lower than that of a previously reported CPE modified with [Ru(phend)(2)bpy](2+)-intercalated ZrP. (1) To improve the characteristics of NADH electrooxidation of the [Co(tpy)(2)](3+):ZrP-modified CPE, we included the enzyme diaphorase in solution, which increased the electrocatalytic current for NADH oxidation. A bienzymatic lactate biosensor was constructed and used for lactate sensing.

NADH Electrooxidation Using Bis(1,10-phenanthroline-5,6-dione) (2,2'-bipyridine)ruthenium(II)-Exchanged Zirconium Phosphate Modified Carbon Paste Electrodes.

We present a carbon paste electrode (CPE) modified using the electron mediator bis(1,10-phenanthroline-5,6-dione) (2,2'-bipyridine)ruthenium(II) ([Ru(phend)(2)bpy](2+)) exchanged into the inorganic layered material zirconium phosphate (ZrP). X-Ray powder diffraction showed that the interlayer distance of ZrP increases upon [Ru(phend)(2)bpy](2+) intercalation from 10.3 Å to 14.2 Å. The UV-vis and IR spectroscopies results showed the characteristic peaks expected for [Ru(phend)(2)bpy](2+). The UV-vis spectrophotometric results indicate that the [Ru(phend)(2)bpy](2+) concentration inside the ZrP layers increased as a function of the loading level. The exchanged [Ru(phend)(2)bpy](2+) exhibited luminescence even at low concentration. Modified CPEs were constructed and analyzed using cyclic voltammetry. The intercalated mediator remained electroactive within the layers (E°' = -38.5 mV vs. Ag/AgCl, 3.5 M NaCl) and electrocatalysis of NADH oxidation was observed. The kinetics of the modified CPE shows a Michaelis -Menten behavior. This CPE was used for the oxidation of NADH in the presence of Bakers' yeast alcohol dehydrogenase. A calibration plot for ethanol is presented.